Surface-modified metal oxide particle material, dispersion liquid, silicone resin composition, silicone resin composite body, optical semiconductor light emitting device, lighting device, and liquid crystal imaging device

Active Publication Date: 2015-10-01
SUMITOMO OSAKA CEMENT CO LTD
15 Cites 14 Cited by

AI-Extracted Technical Summary

Problems solved by technology

Meanwhile, while the silicone resins are excellent in durability, there is involved such a problem that gas permeability is ...
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Method used

[0024]Although the kind of the metal oxide particle is not particularly limited, a kind capable of obtaining a particle diameter of a nanometer size is preferred from the viewpoint of keeping transparency of a sealing material or the like, and examples thereof include zinc oxide, zirconium oxide, titanium oxide, silicon dioxide (silica), aluminum oxide, and the like. In addition, in the case of taking into consideration the matter that a refractive index of the sealing material or the like is increased to enhance light extraction efficiency from an optical semiconductor light emitting device using the sealing material, thereby achieving high luminance, the refractive index of the metal oxide particle is preferably 1.5 or more, more preferably 1.7 or more, and still more preferably 1.9 or more. As such a metal oxide particle, titanium oxide or zirconium oxide (zirconia) is preferred, with zirconia being especially preferred.
[0034]The reasons why the phenyl group is contained in the surface-modifying material reside in the matters that an interfacial affinity for a phenyl silicone resin and a methyl phenyl silicone resin serving as a matrix (these will be hereinafter sometimes referred to summarizingly as “(methyl) phenyl silicone resin”) can be ensured; and that in view of the fact that the surface-modified metal oxide particle and the (methyl) phenyl silicone resin come close to each other due to π-π stacking between the phenyl group of the surface-modifying material and the phenyl group of the (methyl) phenyl silicone resin, a space in the silicone resin composite can be reduced, and the gas permeability can be suppressed.
[0035]The reasons why the alkenyl group is contained in the surface-modifying material reside in the matters that during polymerization and curing of the silicone resin composition, the alkenyl group in the surface-modifying material and the hydrogen group in the silicone resin-forming component serving as a matrix (H (hydrogen) bound directly to Si of the siloxane polymer) can be bound to each other due to the crosslinking reaction (hydrosilylation reaction), and phase separation between the surface-modified metal oxide particle material and the matrix silicone resin in the process of polymerization and curing can be prevented from occurring. In addition, this is because when the surface-modified metal oxide particle material and the matrix silicone resin undergo a crosslinking reaction, the surface-modified metal oxide particle material and the matrix silicone resin come close to each other, a space in the silicone resin composite can be reduced, and the gas permeability can be suppressed.
[0036]Furthermore, by using the surface-modifying material which is excellent in heat resistance, a lowering of transmittance to be caused due to the generation of particle aggregation at high temperatures (lowering of the particle dispersibility), or the generation of coloration of a surface treatment agent itself, can be suppressed, and therefore, the gas permeability can be suppressed without impairing the heat resistance of the matrix silicone resin. Incidentally, the terms “excellent in heat resistance” as referred to herein mean that the surface-modified structure does not change after a thermal loading test (at 150° C. for 1000 hours) (namely, there is freed from the matter that the surface-modified metal oxide particle material in the resin composition causes aggregation by thermal loading, whereby the dispersibility changes, or the matter that the surface-modifying material in the resin composition or resin composite causes coloration by thermal loading), and the same is also applicable to the following.
[0045]Of these, vinyltrimethoxysilane, a dimethyl silicone having an alkoxy introduced into one end thereof and having vinyl introduced into the other end thereof, and materials having a structure in which the hydrocarbon chain of the formula (3) is branched, or a structure in which an alkenyl group is contained on the branched hydrocarbon chain are preferred from the viewpoint that they are also excellent in heat resistance.
[0053]By containing a phenyl group and a hydrogen group in the surface-modifying material in this way, consistency between the surface-modifying material and the matrix silicone resin including a (meth) phenyl silicone resin is enhanced to achieve integration, whereby a lowering of transmittance to be caused due to particle aggregation during thermal loading can be suppressed. In addition, since it is not necessary to make an epoxy group or a vinyl group present, a cause itself for coloration during thermal loading can be removed. Furthermore, the phenyl group itself is high in heat resistance. In the light of the above, the surface-modifying material in the present invention has high heat resistance in itself.
[0055]In this way, by using the surface-modifying material having excellent heat resistance, the gas permeability can be suppressed without impairing the heat resistance of the matrix silicone resin.
[0069]As described previously, during polymerization and curing of the silicone resin composition, the alkenyl group in the surface-modifying material can be bound to and integrated with the hydrogen group in the matrix silicone resin-forming component through a crosslinking reaction (hydrosilylation reaction). In addition, during polymerization and curing of the silicone resin composition, the hydrogen group in the surface-modifying material can be bound to and integrate with the alkenyl group or alkynyl group in the matrix silicone resin-forming component through a crosslinking reaction (hydrosilylation reaction). Then, according to this binding action, not only phase separation between the surface-modified metal oxide particle material and the matrix silicone resin in the process of polymerization and curing can be prevented from occurring, but also by allowing the surface-modified metal oxide particle material and the matrix silicone resin to come close to each other, a space in the silicone resin composite can be reduced, and the gas permeability can be suppressed.
[0074]A surface modification amount of the above-described surface-modifying material relative to the metal oxide particle ((surface-modifying material)/(metal oxide particle)) is preferably from 5 to 40% by mass. So long as the surface modification amount falls within this range, the dispersibility of the surface-modified metal oxide particle material in the silicone resin as described later can be kept high, and a lowering of transparency or gas permeability can be suppressed.
[0080]In addition, for the purpose of enhancing the dispersibility of the particle material or stabilizing the dispersion liquid, the dispersion liquid of the present invention may contain a dispersant, a surface treatment agent, a water-soluble binder, or the like (a dispersant or the like) within the range where its characteristics are not impaired.
[0096]According to this silicone resin composition, the hydrogen group in the silicone resin-forming component undergoes a crosslinking reaction with the alkenyl group of the surface-modifying material to achieve integration, thereby preventing phase separation between the surface-modified metal oxide particle material and the matrix silicone resin in the process of polymerization and curing from occurring; and furthermore, the surface-modified metal oxide particle material and the matrix silicone resin come close to each other, whereby a space in the silicone resin composite can be reduced, and the gas permeability can be suppressed.
[0101]According to this silicone resin composition, the alkenyl group or alkynyl group in the silicone resin-forming component and the hydrogen group of the surface-modifying material undergo a crosslinking reaction (hydrosilylation reaction) to achieve integration, thereby preventing phase separation between the surface-modified metal oxide particle material and the matrix silicone resin in the process of polymerization and curing from occurring; and furthermore, the surface-modified metal oxide particle material and the matrix silicone resin come close to each other, whereby a s...
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Benefits of technology

[0019]According to the present invention, it is possible to provide a surface-modified metal oxide particle material which when used for a sealing material for optical semiconductor light emitting device, or the like, has high heat resistance (namely, coloration during thermal loading or a lowering of transmittance to be caused due to particle aggregation during thermal loading is suppressed) and may further exhibit high transparency and gas barrier properties; a dispersion liquid, a silicone resin composition and a silico...
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Abstract

By using a surface-modified metal oxide particle material obtained by performing surface modification on a metal oxide particle having an average primary particle diameter of 3 nm or more and 10 nm or less with a surface-modifying material having at least a phenyl group and a group capable of undergoing a crosslinking reaction with a functional group in a silicone resin-forming component, the surface-modified metal oxide particle material which has high heat resistance and may further exhibit high transparency and gas barrier properties when used for a sealing material for optical semiconductor light emitting device, or the like is provided and a dispersion liquid, a silicone resin composition and a silicone resin composite each containing the surface-modified metal oxide particle material, as well as an optical semiconductor light emitting device, a light fitting, and a liquid crystal imaging device each using the silicone resin composite, are also provided.

Application Domain

SilicaGlass/slag layered products +11

Technology Topic

Silicone resinOxide +12

Image

  • Surface-modified metal oxide particle material, dispersion liquid, silicone resin composition, silicone resin composite body, optical semiconductor light emitting device, lighting device, and liquid crystal imaging device
  • Surface-modified metal oxide particle material, dispersion liquid, silicone resin composition, silicone resin composite body, optical semiconductor light emitting device, lighting device, and liquid crystal imaging device
  • Surface-modified metal oxide particle material, dispersion liquid, silicone resin composition, silicone resin composite body, optical semiconductor light emitting device, lighting device, and liquid crystal imaging device

Examples

  • Experimental program(14)

Example

[0157]In Examples A1 to A5 and Comparative Examples A1 to A4, heat resistance of a silicone resin composite was evaluated by applying a load to the above-described composite (cured material) having a thickness of 0.5 mm in an electric furnace at 150° C. for 500 hours and then measuring a transmittance using a spectrophotometer (integrating sphere). The case where a transmittance at a wavelength of 450 nm after thermal loading was reduced by 30% or more as compared with an initial value (before thermal loading) was defined as “B”, and the case where a reduction amount was less than 30% was defined as “A”.

Example

[0158]Meanwhile, in Examples B1 to B5 and Comparative Examples B1 to B6, the evaluation was performed by using a composite (thickness: 0.5 mm) of each of the Examples formed on a glass base material and using a spectrophotometer (integrating sphere) to measure a transmittance. Specifically, a silicone resin composite was put into a dryer at 120° C., and after elapsing 1,000 hours, a transmittance at 450 nm was compared with an initial transmittance. The case where a reduction rate of transmittance relative to the initial value was less than 5% was defined as “A”; the case where it was 5% or more and less than 25% was defined as “B”; and the case where it was 25% or more was defined as “C”.
(Gas Permeability (Gas Barrier Properties) of Silicone Resin Composite)
[0159]Gas permeability (gas barrier properties) of a silicone resin composite was evaluated in the following manner.
[0160]First of all, an LED package having a silver-plated reflector was sealed with a silicone resin composition, and the silicone resin composition was cured by a thermal treatment at 150° C. for 3 hours, thereby obtaining a composite of each of the Examples. The resulting package was hermetically sealed together with 0.3 g of a sulfur powder in a 500-mL pressure-resistant glass container and kept at 80° C. An appearance change with time of the silver-plated reflector (corrosion (blackening discoloration) of silver plate by sulfur gas) was observed through visual inspection. In Examples A1 to A5 and Comparative Examples A1 to A4, the case where as compared with the silicone resin not containing a metal oxide particle (Comparative Example A1), the discoloration was slow, and a time required for assuming the equal blackening was 1.5 times or more was evaluated to be low in gas permeability and defined as “A”; the case where as compared with the silicone resin, while the discoloration was slow, a time required for assuming the equal blackening was less than 1.5 times was defined as “B”; and the case where the silver plate was discolored equally to or faster than the silicone resin was defined as “C”.

Example

[0161]Meanwhile, in Examples B1 to B5 and Comparative Examples B1 to B6, blackening of an appearance of the above-described silver-plated reflector (corrosion (blackening discoloration) of silver plate by sulfur gas) was observed through visual inspection and evaluated in terms of a time required for reaching the same degree as that in a separately fabricated standard plate (plate prepared by blackening a silver-plated reflector directly with a sulfur gas). Incidentally, the lower the gas barrier properties of the composite, the shorter the time required for reaching blackening was.
(Hardness Evaluation of Silicone Resin Composite)
[0162]With respect to the hardness evaluation of a silicone resin composite, at the time of fabricating a silicone resin composite, the case where no crack was generated was defined as “A”, and the case where a crack was generated was defined as “B” (Examples B1 to B5 and Comparative Examples B1 to B6).
(Thickness of Sealing Layer Made of Silicone Resin Composite)
[0163]A thickness of a sealing layer made of a silicone resin composite was measured by observing a cross section of the above-described package by SEM.
Example A1
Fabrication of Zirconia Particle
[0164]To a zirconium salt solution of 2,615 g of zirconium oxychloride octahydrate dissolved in 40 L (liters) of pure water, dilute ammonia water of 344 g of 28% ammonia water dissolved in 20 L of pure water was added while stirring, thereby preparing a zirconia precursor slurry.
[0165]Subsequently, a sodium sulfate aqueous solution of 300 g of sodium sulfate dissolved in 5 L of pure water was added to this slurry while stirring. At this time, the addition amount of sodium sulfate was 30% by mass relative to a zirconia conversion value of a zirconium ion in the zirconium salt solution.
[0166]Subsequently, this mixture was dried in the air at 130° C. for 24 hours by using a dryer, thereby obtaining a solid.
[0167]Subsequently, this solid was pulverized by an automatic mortar and then baked in the air at 500° C. for one hour by using an electric furnace.
[0168]Subsequently, this baked material was put into pure water and stirred to make into a slurry form. Thereafter, cleaning was performed using a centrifugal separator, and the added sodium sulfate was sufficiently removed, followed by drying with a dryer, thereby obtaining a zirconia particle having an average primary particle diameter of 4 nm.
(Surface Modification on Zirconia Particle: Fabrication of Surface-Modified Zirconia Particle)
[0169]Subsequently, to 10 g of the zirconia particle, 82 g of toluene and 5 g of a methoxy group-containing phenyl silicone resin (KR217, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed, and the mixture was subjected to a surface modification treatment with a bead mill for 6 hours, followed by removing the beads. Subsequently, 3 g of vinyltrimethoxysilane (KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the contents were subjected to surface modification and dispersion treatment under refluxing at 130° C. for 6 hours, thereby preparing a transparent dispersion liquid of zirconia particle having been surface-modified with a surface-modifying material having a phenyl group and a surface-modifying material having a vinyl group that is an alkenyl group.
(Fabrication of Silicone Resin Composition)
[0170]To 50 g of the above-described transparent dispersion liquid of zirconia particle, 7.6 g of, as a phenyl silicone resin, a trade name: OE-6520 (manufactured by Dow Corning Toray Co., Ltd., refractive index: 1.54, compounding ratio of liquid A/liquid B=1/1) (liquid A: 3.8 g, liquid B: 3.8 g) was added, and after stirring, the toluene was removed by drying under reduced pressure, thereby obtaining a silicone resin composition containing a surface-modified zirconia particle, a phenyl silicone resin, and a reaction catalyst (zirconia particle content: 30% by mass).
[0171]Incidentally, with respect to OE-6520, not only the presence of an Si—H bond is already confirmed by means of an NMR analysis, but also it is already grasped that a hydrogen group is contained in the silicone resin-forming component. In consequence, OE-6520 can be integrated with the vinyl group (alkenyl group) of vinyltrimethoxysilane that surface-modifies the zirconia particle through a crosslinking reaction.
[0172]In addition, with respect to OE-6520, not only the presence of a C═C double bond (vinyl group) that is an alkenyl group is already confirmed by means of an NMR analysis, but also the presence of platinum is already confirmed by means of an emission analysis. That is, OE-6520 is a silicone resin of an addition curing type, which is polymerized and cured by means of an addition reaction (hydrosilylation reaction). In consequence, it can be understood that in OE-6520, not only the vinyl group in the zirconia particle surface-modifying material and the hydrogen group in OE-6520 are bound to each other through a crosslinking reaction in the presence of platinum as a catalyst, but also the vinyl group and the hydrogen group in OE-6520 undergo an addition reaction, whereby the silicone resin-forming component is polymerized and cured in a state of keeping the dispersed state of the zirconia particle.
(Fabrication of Silicone Resin Composite)
[0173]The above-described silicone resin composition was cured by a thermal treatment at 150° C. for 3 hours, thereby obtaining a silicone resin composite.
[0174]The already-described various evaluations were performed by using this silicone resin composite. Incidentally, in the evaluation of gas permeability, the thickness of the sealing layer was made to be 500 μm.
Example A2
Fabrication of Zirconia Particle
[0175]A zirconia particle was fabricated in the same manner as that in Example A1.
(Fabrication of Surface-Modifying Material Containing Both a Phenyl Group and an Alkenyl Group)
Preparation of Surface-Modifying Material A: (CH2═CM(CH3)2SiO(SiO(C6H5)2)45Si(OC2H5)3
[0176]1.8 g of dimethyl vinyl silanol was dissolved in 60 mL of a tetrahydrofuran (THF) solvent in a nitrogen atmosphere, 1.2 g of n-butyl lithium dissolved in n-hexane was added dropwise at a temperature of 0° C. while stirring, and the contents were allowed to react with each other for 3 hours, thereby obtaining lithium dimethyl vinyl silanolate (see formula (A)).
[0177]Subsequently, a solution of 160.5 g of hexaphenyl cyclotrisiloxane dissolved in a THF solvent was added dropwise, and the contents were allowed to react with each other at a temperature of 0° C. for 12 hours, thereby obtaining lithium phenylvinyl organosilanolate (see formula (B)).
[0178]Subsequently, 3.6 g of chlorotriethoxysilane was added, and the contents were allowed to react with each other at a temperature of 0° C. for 12 hours (see formula (C)).
[0179]Subsequently, n-hexane was mixed to form a precipitate of lithium chloride, and thereafter, the lithium chloride was removed by filtration, thereby obtaining a surface-modifying material A containing both a phenyl group and an alkenyl group.
[0180]A structure of the obtained surface-modifying material was confirmed by means of 1H-NMR.
[0181]Here, an outline of the synthesis flow of the surface-modifying material containing both a phenyl group and an alkenyl group is shown below.
(Surface Modification on Zirconia Particle: Fabrication of Surface-Modified Zirconia Particle)
[0182]Subsequently, to 10 g of the zirconia particle, 80 g of toluene and 5 g of a methoxy group-containing phenyl silicone resin (KR217, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed, and the mixture was subjected to a surface modification treatment with a bead mill for 6 hours, followed by removing the beads. Subsequently, 3 g of the above-described surface-modifying material A was added, and the contents were subjected to surface modification and dispersion treatment under refluxing at 130° C. for 6 hours, thereby preparing a transparent dispersion liquid of zirconia particle having been surface-modified with a surface-modifying material having a phenyl group and a surface-modifying material having both a phenyl group and an alkenyl group (vinyl group).
(Fabrication of Silicone Resin Composition and Silicone Resin Composite)
[0183]A silicone resin composition and further a silicone resin composite were fabricated in the same manners as those in Example A1, except for using the above-described methoxy group-containing phenyl silicone resin and the transparent dispersion liquid of zirconia particle having been surface-modified with the surface-modifying material A, followed by performing the various evaluations.
Example A3
[0184]A silicone resin composition and further a silicone resin composite were fabricated in the same manners as those in Example A1, except for making the thickness of the sealing layer to be 30 μm, followed by performing the various evaluations.
Example A4
Fabrication of Titania Particle
[0185]242.1 g of titanium tetrachloride and 111.9 g of tin(IV) chloride pentahydrate were put into 1.5 L (liters) of pure water at 5° C., and the contents were stirred to fabricate a mixed solution.
[0186]Subsequently, this mixed solution was heated to adjust the temperature at 25° C., and an ammonium carbonate aqueous solution having a concentration of 10% by mass was added to this mixed solution, thereby adjusting a pH at 1.5. Thereafter, the resultant was aged at 25° C. for 24 hours, and thereafter, an excessive chloride ion was removed by means of ultrafiltration.
[0187]Subsequently, water was removed from the mixed solution after removal of a chloride ion by using an evaporator, followed by drying to fabricate a titanium oxide particle. The obtained titanium oxide particle had an average primary particle diameter of 4 nm.
[0188]A titania transparent dispersion liquid was fabricated by performing the surface modification, and subsequently, a silicone resin composition and further a silicone resin composite were fabricated in the same manners as those in Example A1, except for using the foregoing titanium particle, followed by performing the various evaluations.
Example A5
Fabrication of Silica Particle
[0189]80 g of methanol was mixed with 20 g of ammonia water having a concentration of 24%, 0.8 g of 10N—NaOH, and 4 g of a polyoxyethylene alkyl ether (a trade name: EMULGEN 707, manufactured by Kao Corporation) as a surfactant. 4 g of tetraethyl silicate (a trade name: ETHYL SILICATE 28, manufactured by Colcoat Co., Ltd.) diluted with methanol was added dropwise thereto. The mixed liquid was stirred at 20° C. for one hour. After completion of stirring, a precipitate was separated by means of decantation, and an operation of redispersion in methanol and decantation was repeated, thereby removing residual ions.
[0190]The obtained wet silica particle was dried under reduced pressure to dry the methanol, thereby obtaining a formed silica particle. The obtained silica particle had an average primary particle diameter of 4 nm.
[0191]A silica transparent dispersion liquid was fabricated by performing the surface modification, and subsequently, a silicone resin composition and further a silicone resin composite were fabricated in the same manners as those in Example A1, except for using the silica particle, followed by performing the various evaluations.

PUM

PropertyMeasurementUnit
Thickness5.0E-5m
Percent by mass5.0mass fraction
Nanoscale particle size3.0nm

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